JP2005163149A - Three-dimensional high-frequency plasma cvd apparatus and three-dimensional high-frequency plasma cvd method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new high-frequency plasma CVD method for three-dimensionally depositing a thin film uniformly at high speed on the surface of a substrate of a mechanical component made of metal or glass or plastic bottle etc. <P>SOLUTION: A pair of high-frequency antenna coils 5 and 5 are arranged apart from and opposite to each other within a vacuum chamber 2 into which gaseous raw materials are introduced. A plasma is generated within the vacuum chamber 2 by applying a high-frequency voltage or pulse voltage to the pair of the high-frequency antenna coils 5 and 5 and the substrate S having a three-dimensional shape on the surface is charged into the space between the pair of the high-frequency antenna coils 5 and 5 to form the deposited film on the surface of the substrate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a three-dimensional high-frequency plasma CVD apparatus and a three-dimensional high-frequency plasma CVD method for forming a thin film three-dimensionally and uniformly on the surface of a base material such as a plastic container.

  Conventionally, for example, aluminum cans have been used as containers for beer and carbonated drinks due to gas barrier properties, and some PET bottles with DLC inner surface coating are practically used as beer containers. It is believed that plastic bottles cannot be used. In addition, as a container for various new drugs such as bio-new drugs, there is a high possibility of plastic bottles that are easy to handle with little risk of breaking and have a high degree of freedom in form, but requires high gas barrier properties and moisture resistance. Currently, glass bottles are used for the drugs to be used. In order to overcome this situation and further improve the functionality of plastic containers, surface treatment technology using plasma has been developed in recent years. Also, surface treatment technology using plasma has been developed in the fields of various mechanical parts made of metal or glass.

For example, Patent Document 1 discloses a technique for strengthening the inner surface of a bottle using plasma, and Patent Document 2 includes a plastic bottle disposed inside a cylindrical electrode, and a rod-shaped electrode disposed in the bottle. A simple plasma CVD method is disclosed in which a raw material gas is introduced into a bottle and plasma is generated inside the bottle by high frequency discharge to form a thin film on the inner surface of the bottle.
Special table 2001-518685 gazette JP 2001-310960 A

All of the techniques described in these documents are to form a silicon oxide film or a carbon film on the inner surface of the bottle, but cannot form a thin film on the bottle surface (outer surface). In addition, such a technique has a low plasma density, and a carbon-based film such as DLC or CH ₄ or a silicon oxide-based film such as hexamethyldisiloxane (hereinafter referred to as “HMDSO”) has a low film formation rate, and is suitable for mass production. There is a problem of not.

  There are various conventional large-sized plasma CVD apparatuses capable of forming a film at a practical speed. However, when forming a film on the surface of a plastic container, it is necessary to maintain a relatively low temperature range. Is not available. In addition, so-called parallel plate type plasma CVD is common, but the distance between the electrodes is only about 5 cm at most, and a three-dimensional container such as a plastic bottle cannot be disposed between the electrodes.

  Meanwhile, Yamashita, one of the inventors of the present application, has already devised a surface treatment technique using inductively coupled high-frequency discharge plasma, for example, M. Yamashita: J. Vac. Sci. Techonol., A7, (1989) 151. Yamashita: J. Vac. Sci. Jpn (vacuum), Vol. 44, No. 5, (2001) 32. This disclosed technique is an inductively coupled plasma sputtering apparatus in which a high-frequency antenna coil is installed between a flat target and a substrate holding base for holding a substrate, and a matching box is connected to the high-frequency antenna coil from the high-frequency power supply device. A high-density plasma is generated by supplying high-frequency power via an (impedance matching circuit).

Such inductively coupled high-frequency discharge plasma is generated exclusively by high-frequency power supplied to a high-frequency antenna coil, and the generated plasma is confined in the coil, and is not required to form a special magnetic circuit around the target, and is 10 ¹² / cm. There are advantages that a high plasma density of ³ or more can be obtained, and that a large space for confining plasma can be secured by appropriately setting the size of the coil. Therefore, it is considered that a thin film can be vapor-phase-grown at high speed on the surface of a substrate such as a plastic bottle by diverting the above inductively coupled high-frequency discharge plasma generation principle to a plasma CVD apparatus.

  However, it is not just that a thin film needs to be formed. In addition to eliminating pinholes in the formed thin film, the thin film formed on its three-dimensional surface is not only used to guarantee the gas barrier properties and moisture resistance of the bottle. Uniformity in film thickness and film quality is required.

  Therefore, an object of the present invention is to provide a novel three-dimensional high-frequency plasma CVD apparatus and a three-dimensional high-frequency plasma CVD method capable of forming a thin film at high speed and uniformly on a three-dimensional surface of a substrate such as a plastic bottle.

  The three-dimensional high-frequency plasma CVD apparatus of the present invention includes a vacuum chamber, a gas supply pipe for supplying a source gas into the vacuum chamber, an exhaust pipe for exhausting the gas in the vacuum chamber so as to keep the inside of the vacuum chamber at a predetermined pressure, A high-frequency antenna coil disposed in the vacuum chamber to generate plasma in the vacuum chamber, a power supply circuit for applying high-frequency power or pulse power to the high-frequency antenna coil, and a surface in the plasma generated by the high-frequency antenna coil Includes a three-dimensional shape base material supporting member that supports a base material having a three-dimensional shape.

  As the high-frequency antenna coil, a circular coil can be suitably used, and a coil that is curved so as to surround the base material charging space in three dimensions can also be used. The number of turns of the circular coil is not particularly limited as long as the required plasma density is obtained, but about 3 to 8 turns are preferable. As a material of the high-frequency antenna coil, an aluminum material can be suitably used, and other appropriate materials such as copper and carbon can be adopted. This high-frequency antenna coil is in contact with the plasma because it is installed in the vacuum chamber, but an ion sheath is formed near the surface of the coil, thereby galvanically insulating the coil windings and between the coil and ground. In addition, it is possible to maintain high frequency. The high frequency antenna coil itself constitutes an impedance matching circuit. In addition, it is possible to cool a coil by comprising a high frequency antenna coil by a tubular member and distribute | circulating a refrigerant | coolant in this coil.

  The power supply circuit supplies high frequency power or pulse power to the high frequency antenna coil, thereby generating high frequency plasma. The oscillation frequency of this power supply circuit can be 4 MHz to 50 MHz, and the maximum output is about 1 kW. The power incident on the antenna coil during film formation depends on the type of source gas, the structure and size of the vacuum chamber, and the characteristics of the high frequency antenna coil. For example, it can be made appropriate. When a pulse voltage is applied to the high-frequency antenna coil using a pulse oscillator as a power supply circuit, an increase in the atmospheric temperature in the chamber can be suppressed, which is suitable when a plastic container is used as a base material. Further, the plasma density in the vacuum chamber can be significantly increased by changing the phase of the high-frequency voltage applied to the pair of high-frequency antenna coils by 180 degrees. In addition, the value of the high-frequency voltage applied to both coils can be changed independently, which can change the plasma density distribution in the vacuum chamber, and at the same time as improving the film formation rate, Control can also be performed.

  The shape of the three-dimensional surface of the base material can be appropriate, in addition to those having a peripheral surface and a bottom surface like a plastic bottle, those having a peripheral surface like a tube, a mountain shape, and uneven grooves Examples thereof include a plate member.

  According to the three-dimensional high-frequency plasma CVD apparatus of the present invention, since the base material is supported in the high-density plasma generated by applying a high-frequency voltage or pulse voltage to the high-frequency antenna coil, the entire three-dimensional surface of the base material is supported. The plasma density is homogenized throughout, and a thin film is formed on the three-dimensional surface at high speed and uniformly.

  In order to confine the plasma more efficiently, it is preferable to arrange a shielding plate for plasma shielding outside the high frequency antenna coil. According to this, the dispersion of the plasma in the chamber is relaxed, and the plasma is concentrated in the center of the chamber, so that the film formation speed and the thin film uniformity can be improved. The plasma density can also be improved by controlling the magnetic field in the chamber by installing a magnet at an appropriate location on the outer periphery of the vacuum chamber. A hole can be provided in the central portion of the plasma shielding plate, and if this hole is made small, the plasma is almost completely confined in the antenna coil to further increase its density.

  Further, in order to improve the uniformity of the thin film, a porous electrode surrounding the substrate and an ion energy control power source for applying a high frequency voltage to the porous electrode can be further provided. According to this, it is possible to control the ion energy in the plasma according to the surface shape of the base material and to further improve the quality of the thin film to be formed.

  More preferably, at least a pair of the high-frequency antenna coils are provided and each high-frequency antenna coil is a circular coil, and the pair of high-frequency antenna coils are spaced apart from each other in a vacuum chamber and supported by the support member. Can be introduced into the space between the pair of high frequency antenna coils. According to this, the plasma generated by each high-frequency antenna coil is fused at the center of the pair of coils, so that the plasma density can be further increased and made uniform and the plasma can be confined in a relatively wide space. It becomes possible. Further, a wide space where plasma is generated is formed between the pair of coils, and a large base material can be put into this space. Therefore, a thin film can be formed at a high speed by a high-frequency plasma CVD method on a relatively large base material such as a plastic bottle.

  The support member can be configured to be capable of reciprocating so that the base material is inserted into and removed from the space between the pair of high-frequency antenna coils. According to this, a three-dimensional base material can be easily installed between a pair of coils, and can be easily taken out even after film formation.

  In the above-described three-dimensional high-frequency plasma CVD apparatus of the present invention, the high-frequency power or pulse power may be supplied to each high-frequency antenna coil so that the direction of the magnetic lines of force are the same at the same point. The high frequency power or pulse power may be supplied to each high frequency antenna coil so that the direction of the magnetic lines of force is reversed at the same point. By controlling the direction of the lines of magnetic force in this way, a further improvement in plasma density can be expected due to a synergistic effect.

  The power supply circuit may include a DC power supply device that applies a bias voltage to the high-frequency antenna coil. By applying such a bias voltage, a synergistic effect on plasma electron motion is generated between the pair of antenna coils, and the plasma density can be increased. Further, this bias voltage may be applied to each high-frequency antenna coil so that the direction of the magnetic field lines is the same direction, or applied to each high-frequency antenna coil so that the magnetic field lines are directed toward the center of the pair of high-frequency antenna coils. Also good.

  In the device of the present invention, two or three pairs of high frequency antenna coils may be provided. In this case, it is preferable to arrange each pair of high-frequency antenna coils opposite to the substrate in different directions so as to surround the substrate. According to this, it is possible to generate a higher-density plasma by a plurality of pairs of high-frequency antenna coils, and it is possible to perform dramatic improvement in film formation and uniform thin film formation over the entire circumference of the substrate. Become. In this case, a source gas supply pipe and an exhaust pipe can be provided for each pair of high-frequency antenna coils.

  In the three-dimensional high-frequency plasma CVD method of the present invention, at least a pair of high-frequency antenna coils are spaced apart from each other in a vacuum chamber into which a source gas is introduced, and high-frequency power or pulse power is supplied to the high-frequency antenna coils. In this way, plasma is generated in the vacuum chamber, and a substrate having a three-dimensional surface is inserted between the pair of high frequency antenna coils, so that the tertiary of the substrate is generated in the plasma generated between the pair of high frequency antenna coils. A thin film is vapor-phase grown on the original surface. In the three-dimensional high-frequency plasma CVD method of the present invention, a high-frequency antenna coil is disposed in a vacuum chamber into which a source gas is introduced, and plasma is generated in the vacuum chamber by supplying high-frequency power or pulse power to the high-frequency antenna coil. In addition, a substrate having a three-dimensional surface is introduced into the high-frequency antenna coil, and a thin film is vapor-phase grown on the three-dimensional surface of the substrate in plasma generated inside the high-frequency antenna coil.

  In the three-dimensional high-frequency plasma CVD method, by enclosing a base material with a porous electrode and applying a high-frequency voltage to the porous electrode, ion energy in the plasma related to the base material surface can be controlled.

  Further, the high frequency power or pulse power can be supplied to each high frequency antenna coil so that the direction of the magnetic lines of force are the same at the same point.

  In addition, the high frequency power or pulse power can be supplied to each high frequency antenna coil so that the direction of the magnetic lines of force is reversed at the same point.

  In addition, a bias voltage can be applied to each high-frequency antenna coil so that the direction of the lines of magnetic force are the same.

  Further, a bias voltage may be applied to each high-frequency antenna coil such that the magnetic field lines are directed toward the center of the pair of high-frequency antenna coils.

  Two or three high frequency antenna coils are provided, and each pair of high frequency antenna coils is opposed to the base material in different directions so as to surround the base material, and high frequency power or pulse power is applied to the high frequency antenna coils. It is also possible to form a thin film on the substrate surface in the plasma generated by supplying.

  The present invention also relates to a plastic container having a thin film formed on the surface thereof by the three-dimensional high-frequency plasma CVD method. Since the plasma CVD method of the present invention forms a film in a high density and uniform plasma over a relatively large space between a pair of high frequency antenna coils, various thin films can be formed at industrially realistic speeds. A film can be formed. For example, according to the present invention, a carbon-based film, a silicon oxide-based film, silicon oxide, silicon nitride, a two-layer structure of silicon oxide and silicon nitride film, a multilayer structure of SiOx-SiOn-SiNx, a gradient of SiOx A film made of or containing various inorganic materials capable of gasifying constituent elements such as a tissue film, TiOx, AlOx, and DLC can be formed. As a material of the plastic container, it can be applied to various plastics such as PET, PE, PP, and COP.

  According to the present invention, since the pair of high frequency antenna coils provided in the vacuum chamber is employed as a plasma generation source for generating high frequency plasma in high frequency plasma CVD, the plasma density can be increased and a three-dimensional shape base can be achieved. A large space that can accommodate the material can be provided in the central portion of the vacuum chamber, and it is possible to concentrate the plasma in this accommodating space, increasing the deposition rate by increasing the density of the plasma, over a wide range The quality of the thin film can be improved by making the plasma density uniform.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the drawings.

  FIG. 1 shows a three-dimensional plasma CVD apparatus 1 according to a first embodiment of the present invention, which includes a vacuum chamber 2, a gas supply pipe 3 for supplying a source gas into the vacuum chamber 2, and a vacuum chamber. An exhaust pipe 4 that exhausts the gas in the vacuum chamber 2 to maintain the inside of the vacuum chamber 2 at a predetermined pressure, and a pair of high-frequency waves that are arranged opposite to each other in the vacuum chamber 2 to generate inductively coupled plasma in the vacuum chamber 2 Antenna coils 5, 5, a power supply circuit 6 that applies a high-frequency voltage to the high-frequency antenna coils 5, 5, and a bottle support that supports a plastic bottle S (base material) in the plasma generated by the high-frequency antenna coils 5, 5 A member 7 (three-dimensional shape substrate support member) and a plasma shielding plate 8 are provided.

  The vacuum chamber 2 has, for example, a cylindrical shape with a diameter of 300 to 500 mm and a height of 300 mm, is made of a metal such as stainless steel, and is grounded. The gas supply pipe 3 is a raw material container attached to the vacuum chamber 2 or a raw material gas supply system for introducing a raw material gas such as methane gas from the raw material gas tank into the vacuum chamber 2 as it is or mixed with a carrier gas such as hydrogen or nitrogen. The tube configuration may be appropriate. In the illustrated embodiment, the gas supply pipe 3 is provided on one side in the axial direction of the pair of high-frequency antenna coils 5 and 5, and the exhaust pipe 4 is provided on the opposite side. The exhaust pipe 4 is connected to a vacuum pump. By vacuuming the inside of the vacuum chamber 2, the pressure in the chamber can be set to a degree of vacuum of about 0.05 Pa to 5 Pa during film formation. .

  The plasma excitation high-frequency antenna coil 5 is formed by, for example, using an aluminum pipe or copper pipe having an outer diameter of 8 mm and an inner diameter of 4 mm and bending it in a spiral shape so as to have a diameter of 150 mm to 250 mm and a winding number of 4 to 8. Can be. By using the pipe, it is possible to cool the coil 5 by circulating a refrigerant through the pipe.

  The pair of high frequency antenna coils 5 and 5 are arranged to face each other so that the plastic bottle S can be inserted therebetween. The separation distance between the pair of coils 5 and 5 may be appropriate. Plasma shielding plates 8 are disposed on both outer sides of the pair of high frequency antenna coils 5 and 5. The plasma shielding plate 8 is made of, for example, a SUS plate material or a mesh grid electrode. The plasma generated by high frequency energy is confined in the pair of antenna coils 5 and 5 to further improve the plasma density.

  The power supply circuit 6 includes a high frequency power supply device 10 having a frequency of 4 MHz, a DC power supply device 11 for applying a bias voltage for sputtering to the high frequency antenna coils 5 and 5, and an impedance matching circuit 12. The pair of high frequency antenna coils 5, 5 are connected in series, and these high frequency antenna coils 5, 5 are connected to the high frequency power supply device 10 via the impedance matching circuit 12, and when the coil 5 is sputtered, a DC power supply device 11 is connected. That is, the apparatus of this embodiment can deposit the coil material on the substrate surface by sputtering simultaneously with the vapor phase growth of the thin film by the CVD method. In order to avoid mutual interference between the high-frequency power supply device 10 and the DC power supply device 11, a low-pass filter (LPF) composed of a capacitor 13 and an inductor 14 is connected to the DC power supply device 11 in series. As the DC power supply device 11, for example, a stabilized power supply that is variable from 0 V to −1000 V can be used.

  According to the wiring connection example of the present embodiment, the phase of the high-frequency power supplied from the high-frequency power supply device 10 to the high-frequency antenna coils 5 and 5 is the same, so the high-frequency power is supplied to the high-frequency antenna coils 5 and 5. The direction of the lines of magnetic force generated by doing so is the same in the axial direction at the same point. The bias voltage applied by the DC power supply device 11 is also applied to each high-frequency antenna coil 5 in the same direction.

  The bottle support member 7 is made of, for example, a rod-shaped member made of stainless steel, and is grounded so that the plastic bottle S is inserted into and removed from the space between the pair of high frequency antenna coils 5 and 5. It is configured to be able to reciprocate by an appropriate drive device such as a fluid pressure cylinder. The method for removing the plastic bottle S may be appropriate. For example, in the illustrated example, a base material input chamber 2a is provided in the center of the vacuum chamber 2, and the plastic bottle S input into the base material input chamber 2a is provided. The supporting member 7 can be configured so that it can be inserted into the space between the pair of high-frequency antenna coils 5 and 5. In order to prevent the plasma from escaping to the base material input chamber 2a, the base material input chamber 2a and the inside of the vacuum chamber may be partitioned by a plasma shielding grid or the like.

In order to form a thin film on the surface of the plastic bottle S by the high frequency plasma CVD method using the apparatus of the above embodiment, after evacuating the vacuum chamber 2, methane gas is introduced into the vacuum chamber 2 and the gas pressure is adjusted. The power supply circuit 6 supplies a predetermined high-frequency power, for example, 150 W of high-frequency power to the high-frequency antenna coils 5 and 5 at a predetermined pressure, for example 0.8 Pa. Then, the discharge of methane gas starts by the high frequency energy generated in the vacuum chamber 2, and the generated plasma is almost completely confined in the pair of high frequency antenna coils 5 and 5, for example, with a high density of 10 ¹² / cm ^3. Become brighter. After the plasma is stabilized, when the support member 7 is driven to put the plastic bottle S into the space between the pair of high frequency antenna coils 5, 5, the plastic bottle S is placed in the space between the pair of high frequency antenna coils 5, 5. Thus, the thin film is vapor-phase grown by the plasma CVD method at high speed and uniformly over the entire surface of the bottle S. Further, since the plastic bottle S can be charged after the plasma is stabilized, a more uniform thin film can be formed.

  FIG. 2 shows a three-dimensional high-frequency plasma CVD apparatus 1 according to the second embodiment of the present invention. The same components as those in the first embodiment are denoted by the same reference numerals, detailed description thereof is omitted, and different configurations are provided. The effect will be described.

  In the present embodiment, by changing the power supply wiring of each antenna coil 5, high-frequency power from the high-frequency power supply device 10 is supplied to each high-frequency antenna coil so that the direction of the magnetic lines of force is reversed at the same point, and direct current The bias voltage by the power supply device 11 is applied to each high-frequency antenna coil in the reverse direction. According to such a configuration, in the space between the pair of antenna coils 5 and 5, the high frequency energy from the antenna coils 5 and 5 on both sides thereof acts to excite plasma so as to spread larger than the coil diameter. Therefore, thin film growth by the plasma CVD method can be performed uniformly and at high speed on the three-dimensional surface of the larger substrate S.

  In the present embodiment, the gas supply pipes 3 are provided at a plurality of locations in the circumferential direction of the vacuum chamber 2 so that the source gas can be uniformly introduced into the vacuum chamber 2 from the plurality of locations in the circumferential direction.

  FIG. 3 shows a three-dimensional high-frequency plasma CVD apparatus 1 according to the third embodiment of the present invention. In this embodiment, a plastic bottle S is interposed between a pair of high-frequency antenna coils 5 and 5 in the vacuum chamber 2. The electrode 14 is connected to an ion energy control power source 15 so that a high frequency voltage or a pulse voltage can be applied to the porous electrode 14. Since other configurations are the same as those of the first embodiment, detailed description thereof is omitted. In FIG. 3, the power supply circuit of the high frequency antenna coil 5 is omitted.

  The porous electrode 14 is made of, for example, a mesh-like metal electrode having an opening ratio of 50% or more, may have a shape that matches the surface shape of the plastic bottle S, and has a size that can accommodate the plastic bottle S. It may have a cylindrical shape. The ion energy control power supply 15 supplies a high frequency power of several kHz to several MHz to the electrode 14, controls the ion energy in the plasma according to the surface shape of the substrate S, and forms a thin film to be formed. It becomes possible to further improve the quality.

  FIG. 4 shows a three-dimensional high-frequency plasma CVD apparatus 1 according to a fourth embodiment of the present invention. In this embodiment, three pairs of high-frequency antenna coils 5 and 5 are arranged orthogonally on three axes. In this way, by making each pair of high-frequency antenna coils 5 and 5 face each other in different directions so as to surround the base material S, the plasma density can be further improved and the three-dimensional plasma can be improved. The uniformity is improved.

  The present invention is not limited to the above-described embodiment, and the design can be changed as appropriate. For example, in each of the above embodiments, it is possible to further improve the plasma density by controlling the magnetic field in the vacuum chamber by disposing a magnet at an appropriate part of the vacuum chamber. Further, there may be only one high-frequency antenna coil. In that case, the base material is introduced into the inside of the high-frequency antenna coil from the side in the axial direction so that the base is formed in the high-density plasma generated inside the high-frequency antenna coil. It is possible to perform vapor phase growth of a thin film on the material surface at high speed.

  The present invention is capable of forming high-quality thin films at high speed on various three-dimensional structures made of metal and glass, as well as plastic bottles for beer and carbonated beverages, drug containers, and bio-new products that are expected to be in great demand in the future. The barrier property of the medicinal container can be remarkably improved, and the moisture resistance and water resistance of the outer surface of the container made of plastic or other suitable material with excellent processability can be secured.

1 is an overall simplified cross-sectional view of a three-dimensional high-frequency plasma CVD apparatus according to a first embodiment of the present invention. It is the whole simplified sectional drawing of the three-dimensional high frequency plasma CVD apparatus which concerns on 2nd Embodiment of this invention. It is the whole simplified sectional drawing of the three-dimensional high frequency plasma CVD apparatus which concerns on 3rd Embodiment of this invention. It is the whole simplified sectional drawing of the three-dimensional high frequency plasma CVD apparatus which concerns on 4th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Three-dimensional high frequency plasma CVD apparatus 2 Vacuum chamber 3 Source gas supply pipe 4 Exhaust pipe 5 High frequency antenna coil 6 Power supply circuit 7 Base material support member 8 Plasma shielding board 10 High frequency power supply apparatus 11 DC power supply apparatus

Claims (13)

A vacuum chamber, a gas supply pipe for supplying a source gas into the vacuum chamber, an exhaust pipe for exhausting the gas in the vacuum chamber to keep the inside of the vacuum chamber at a predetermined pressure, and a vacuum to generate plasma in the vacuum chamber A high frequency antenna coil disposed in the chamber, a power supply circuit for applying high frequency power or pulse power to the high frequency antenna coil, and a substrate having a three-dimensional surface in plasma generated by the high frequency antenna coil In a plasma CVD apparatus comprising a three-dimensional shape substrate support member,
At least one pair of the high-frequency antenna coils is provided, the pair of high-frequency antenna coils are arranged to be opposed to each other in a vacuum chamber, and the base material supported by the support member is put into a space between the pair of high-frequency antenna coils. A three-dimensional high-frequency plasma CVD apparatus.   2. The three-dimensional high-frequency plasma CVD apparatus according to claim 1, further comprising a porous electrode surrounding the substrate and an ion energy control power source for applying a high-frequency voltage or a pulse voltage to the porous electrode.   3. The three-dimensional high-frequency plasma CVD apparatus according to claim 1, wherein the support member is capable of reciprocating so that the base material is inserted into and separated from the space between the pair of high-frequency antenna coils. .   4. The three-dimensional high-frequency plasma CVD apparatus according to claim 1, wherein the high-frequency power or pulse power is applied to each high-frequency antenna coil so that the direction of the lines of magnetic force are the same at the same point.   4. The three-dimensional high-frequency plasma CVD apparatus according to claim 1, wherein the high-frequency power or pulse power is applied to each high-frequency antenna coil so that the direction of the magnetic lines of force is reversed at the same point.   The high frequency antenna coil according to any one of claims 1 to 5, wherein two or three pairs of high frequency antenna coils are provided, and each pair of the high frequency antenna coils is opposed to the base material in different directions so as to surround the base material. A three-dimensional high-frequency plasma CVD apparatus characterized by that.   At least a pair of high frequency antenna coils are spaced apart from each other in the vacuum chamber into which the source gas is introduced, and plasma is generated in the vacuum chamber by supplying high frequency power or pulse power to the high frequency antenna coils. A three-dimensional high-frequency plasma in which a substrate having a three-dimensional surface is inserted between the high-frequency antenna coils and a thin film is vapor-phase grown on the three-dimensional surface of the substrate in the plasma generated between the pair of high-frequency antenna coils CVD method.   8. The tertiary according to claim 7, wherein ion energy in plasma related to the surface of the substrate is controlled by surrounding the substrate with a porous electrode and applying a high frequency voltage or a pulse voltage to the porous electrode. Original high-frequency plasma CVD method.   9. The three-dimensional high-frequency plasma CVD method according to claim 7, wherein the high-frequency power or pulse power is supplied to each high-frequency antenna coil so that the direction of the magnetic lines of force is the same at the same point.   9. The three-dimensional high-frequency plasma CVD method according to claim 7, wherein the high-frequency power or pulse power is applied to each high-frequency antenna coil so that the direction of the magnetic lines of force is reversed at the same point.   The high-frequency antenna coil according to any one of claims 7 to 10, wherein two or three pairs of high-frequency antenna coils are provided, and each pair of high-frequency antenna coils is opposed to the base material in different directions so as to surround the base material. A three-dimensional high-frequency plasma CVD method characterized in that a thin film is vapor-grown on a substrate surface in plasma generated by applying high-frequency power or pulse power to a high-frequency antenna coil.   A high-frequency antenna coil is disposed in a vacuum chamber into which a source gas is introduced, and plasma is generated in the vacuum chamber by supplying high-frequency power or pulse power to the high-frequency antenna coil, and a surface is formed inside the high-frequency antenna coil. A three-dimensional high-frequency plasma CVD method in which a base material having a three-dimensional shape is introduced and a thin film is vapor-phase grown on the three-dimensional surface of the base material in plasma generated inside the high-frequency antenna coil.   A plastic container having a thin film formed on the surface thereof by the three-dimensional high-frequency plasma CVD method according to any one of claims 7 to 12.

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